Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3975359 A
Publication typeGrant
Application numberUS 05/537,173
Publication dateAug 17, 1976
Filing dateDec 30, 1974
Priority dateDec 30, 1974
Also published asCA1067229A1, DE2610152A1
Publication number05537173, 537173, US 3975359 A, US 3975359A, US-A-3975359, US3975359 A, US3975359A
InventorsElmer D. Dickens, Jr.
Original AssigneeThe B. F. Goodrich Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Smoke retardant vinyl chloride and vinylidene chloride polymer compositions
US 3975359 A
Abstract
Smoke retardant vinyl chloride and vinylidene chloride polymer compositions are obtained by including therein a synergistic mixture of (A) at least one nickel compound selected from the group consisting of NiCl2, NiCO3 NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWO4, nickel citrate and nickel formate, and (B) at least one bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3, and Bi2 S3. Substantial smoke retardation is also obtained by including the above nickel compounds or bismuth compounds individually or the following nickel compounds or bismuth compounds individually in the vinyl chloride or vinylidene chlorides polymer compositions: NiB2, NiCrO4, NiFe2 O4, NiI2, Ni3 (PO4)2, Ni2 Si, NiSnO3, nickel acetylacetonate, BiI3, or BiPO4.3H2 O.
Images(6)
Previous page
Next page
Claims(35)
I claim:
1. A smoke retardant composition comprising a vinyl chloride or vinylidene chloride polymer together with (A) at least one nickel compound selected from the group consisting of NiCl2, NiCO3, NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWo4, nickel citrate and nickel formate, and (B) at least one bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3 and Bi2 S3, said compounds (A) and (B) being present in a total amount from about 0.25 to about 20 weight parts per 100 weight parts of polymer.
2. A composition of claim 1 wherein said polymer contains copolymerized therewith up to about 50% by weight of at least one other vinylidene monomer containing at least one terminal CH2 =C< group per molecule.
3. A composition of claim 2 wherein said polymer contains copolymerized therewith up to about 20% by weight of said other vinylidene monomer.
4. A composition of claim 3 wherein said other vinylidene monomer is selected from the group consisting of 1-olefins containing from 2 to 12 carbon atoms, vinyl esters, α,β-olefinically unsaturated carboxylic acids and esters thereof, amides of α,β-olefinically unsaturated carboxylic acids, and esters of fumaric and maleic acid.
5. A composition of claim 4 wherein said compound has an average particle size less than about 200 microns.
6. A composition of claim 5 wherein said compound (A) is NiO and said compound (B) is Bi2 O3.
7. A composition of claim 5 wherein said compound (A) is NiO and said compound (B) is Bi2 O2 CO3.
8. A composition of claim 5 wherein said compound (A) is NiO and said compound (B) is BiBO3.
9. A composition of claim 5 wherein said compound (A) is Ni2 O3 and said compound (B) is Bi2 O2 CO3.
10. A composition of claim 5 wherein said compound (A) is NiS and said compound (B) is Bi2 O2 CO3.
11. A composition of claim 5 wherein said compound (A) is NiWO4 and said compound (B) is Bi2 O2 CO3.
12. A composition of claim 5 wherein said compound (A) is NiCl2 and said compound (B) is Bi2 O2 CO3.
13. A composition of claim 5 wherein said compound (A) is NiCO3 and said compound (B) is Bi2 S3.
14. A composition of claim 5 wherein said compound (A) is NiMoO4 and said compound (B) is Bi2 O2 CO3.
15. A composition of claim 5 wherein said compound (A) is NiSO4 and said compound (B) is Bi2 O2 CO3.
16. A composition of claim 5 wherein said compound (A) is nickel citrate and said compound (B) is Bi2 O2 CO3.
17. A composition of claim 5 wherein said compound (A) is nickel formate and said compound (B) is Bi2 O2 CO3.
18. A smoke retardant composition comprising a vinyl chloride or vinylidene chloride polymer together with a compound selected from the group consisting of NiB2, NiCO3, NiCrO4, NiFe2 O4, Ni3 (PO4)2, NiS, NiSnO3, NiSO4, NiWO4, nickel citrate, BiBO3, Bi2 O2 CO3 and BiPO4.3H2 O, said compound being present in an amount from about 0.25 to about 20 weight parts per 100 weight parts of polymer.
19. A composition of claim 18 wherein said polymer contains copolymerized therewith up to about 50% by weight of at least one other vinylidene monomer containing at least one terminal CH2 =C< group per molecule.
20. A composition of claim 19 wherein said polymer contains copolymerized therewith up to about 20% by weight of said other vinylidene monomer.
21. A composition of claim 20 wherein said other vinylidene monomer is selected from the group consisting of 1-olefins containing from 2 to 12 carbon atoms, vinyl esters, α, β-olefinically unsaturated carboxylic acids and esters thereof, amides of α,β-olefinically unsaturated carboxylic acids, and esters of fumaric and maleic acid.
22. A composition of claim 21 wherein said compound has an average particle size less than 200 microns.
23. A composition of claim 22 wherein said compound is NiB2.
24. A composition of claim 22 wherein said compound is NiCO3.
25. A composition of claim 22 wherein said compound is NiCrO4.
26. A composition of claim 22 wherein said compound is NiFe2 O4.
27. A composition of claim 22 wherein said compound is Ni3 (PO4)2.
28. A composition of claim 22 wherein said compound is NiS.
29. A composition of claim 22 wherein said compound is NiSnO3.
30. A composition of claim 22 wherein said compound is NiSO4.
31. A composition of claim 22 wherein said compound is NiWO4.
32. A composition of claim 22 wherein said compound is nickel citrate.
33. A composition of claim 22 wherein said compound is BiBO3.
34. A composition of claim 22 wherein said compound is Bi2 O2 CO3.
35. A composition of claim 22 wherein said compound is BiPO4.3H2 O.
Description
BACKGROUND OF THE INVENTION

Vinyl chloride and vinylidene chloride polymers are known to be self-extinguishing and relatively more flame retardant than other polymers such as polyethylene, polypropylene and the like. However, a substantial amount of smoke may be produced upon exposure of vinyl chloride and vinylidene chloride polymers to a flame. Conventional flame retardants such as antimony oxide do not aid in smoke reduction.

The following prior art is related to the present invention. Nickel oxides or bismuth oxides are effective in amounts up to several percent as condensing agents for polyvinyl halides. (U.S. Pat. No. 2,157,997). Bismuth oxide is a known vinyl chloride polymer flame retardant, either alone or mixed with certain other materials; see U.S. Pat. No. 2,590,211, U.S. Pat. Off. Def. Publ. 892,010 (76 Chem. Abs. 73666a), 2 Brit. Polym.J. 249-253(1970) (73 Chem. Abs.131605f), and Germ. 1,201,544 (63 Chem. Abs. 15.61e). Bi2 S3 is a known vinyl chloride polymer flame retardant (U.S. Pat. No. 2,590,211). The fact that an additive is a flame retardant does not mean that it will have good smoke retardant properties, as is well known to those skilled in the art. New smoke retardant vinyl chloride and vinylidene chloride polymer compositions are desired.

SUMMARY OF THE INVENTION

Smoke retardant vinyl chloride and vinylidene chloride polymer compositions are obtained by including therein a synergistic mixture of (A) at least one nickel compound selected from the group consisting of NiCl2, NiCO3, NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWO4, nickel citrate and nickel formate and (B) at least one bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3 and Bi2 S3. Substantial smoke retardation is also obtained by including these nickel compounds or bismuth compounds individually in the vinyl chloride or vinylidene chloride polymer compositions: NiB2, NiCl2, NiCO3, NiCrO4, NiFe2 O4, NiI2, NiMoO4, Ni3 (PO4)2, NiS, NiSnO3, NiSO4, NiWO4, nickel citrate, nickel formate, nickel acetylacetonate, BiBO3, BiI3, Bi2 O2 CO3 or BiPO4.3H2 O.

DETAILED DESCRIPTION

The following compounds are novel additives in vinyl chloride and vinylidine chloride polymer compositions and are effective individually as smoke retardants: NiB2, NiCl2, NiCO3, NiCrO4, NiFe2 O4, NiI2, NiMoO4, Ni3 (PO4)2, NiS, NiSnO3, NiSO4, NiWO4, nickel citrate, nickel formate, nickel acetylacetonate, BiBO3, BiI3, Bi2 O2 CO3 or BiPO4.3H2 O. Moreover, the present invention also encompasses vinyl chloride and vinylidene chloride polymer compositions containing therein synergistic mixtures of (A) at least one nickel compound selected from the group consisting of NiCl2, NiCO3, NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWO4, nickel citrate and nickel formate, and (B) at least one bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3, and Bi2 S3.

Vinyl chloride and vinylidene chloride polymers used in this invention include homopolymers, compolymers and blends of homopolymers and/or copolymers. The vinyl chloride and vinylidene chloride polymers may contain from 0 up to about 50% by weight of at least one other vinylidene monomer (i.e., a monomer containing at least one terminal CH2 =C< group per molecule) copolymerized therewith, more preferably up to about 20% by weight of such monomer. These monomers include 1-olefins having from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-hexane, 4-methyl-1-pentene and the like; dienes having from 4 to 10 carbon atoms including conjugated dienes as butadiene, isoprene, piperylene and the like; ethylidene norbornene and dicyclopentadiene; vinyl esters and allyl esters such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, allyl acetate and the like; vinyl aromatics such as styrene, α-methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene and the like; vinyl and allyl ethers and ketones such as vinyl methyl ether, allyl methyl ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl chloroethyl ether, methyl vinyl ketone and the like; vinyl nitriles such as acrylonitrile, methacrylonitrile and the like; cyanoalkyl acrylates such as α-cyanomethyl acrylate, the α-, β- and γ-cyanopropyl acrylates and the like; olefinically unsaturated carboxylic acid and esters thereof, including α,β-olefinically unsaturated acids and esters thereof such as methyl acrylate, ethyl acrylate, chloropropyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hexythioethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate and the like, and including esters of maleic and fumaric acid and the like; amides of the α,β-olefinically unsaturated carboxylic acids such as acrylamide and the like; divinyls, diacrylates and other polyfunctional monomers such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, ethylene glycol dimethacrylate, methylenebis-acrylamide, allyl pentaerythritol, and the like; bis(β-haloalkyl) alkenyl phosphonates such as bis(β-chloroethyl) vinyl phosphonate and the like; and the like.

More preferred monomers include 1-olefins having from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 4-methyl-1-pentene and the like; vinyl esters and allyl esters such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, allyl acetate and the like; olefinically unsaturated carboxylic acids and esters thereof, including α,β-olefinically unsaturated acids and esters thereof such as methyl acrylate, ethyl acrylate, chloropropyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hexylthioacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate and the like, and including esters of maleic and fumaric acid and the like; and amides of α,β-olefinically unsaturated carboxylic acids such as acrylamide and the like.

More preferred smoke retardant synergistic mixtures include (A) at least one nickel compound selected from the group consisting of NiO and Ni2 O3 and (B) at least one bismuth compound selected from the group consisting of Bi2 O3 and Bi2 O2 CO3. More preferred individual smoke retardant additives include NiCO3, NiBO3, and Bi2 O2 CO3. Supporting media such as Al2 O3, SiO2 and other substantially inert inorganic supporting materials known in the art may be used for the smoke retardant additives and in many cases are preferred, since additive surface area is greatly increased for smoke reduction purposes.

Not all nickel compound/bismuth compound mixtures are synergistic, and it is difficult or impossible to predict synergism. Mixtures found to be nonsynergistic include NiB2 and BiPO4.3H2 O, nickel stearate and bismuth salicylate, nickel acetylacetonate and BiI3, and Ni3 (PO4)2 and Bi2 O2 CO3. Other nonsynergistic combinations include nickel metal and bismuth metal, nickel borate and Bi2 O2 CO3, NiCl2 and bismuth metal, and NiO and bismuth metal. Thus, it was surprising and unexpected to find synergistic smoke reduction using the specific nickel compound/bismuth compound mixtures of this invention.

The additive compounds used in this invention are polycrystalline or amorphous fine powders, preferably with an average particle size less than about 200 microns, more preferably from about 0.5 to about 150 microns. Polymer compositions containing the additives of this invention may have colors similar to, although somewhat lighter than, the additives themselves. The additive compounds are used in total amounts from about 0.25 to about 20 parts by weight per 100 parts by weight of polymer. Use of more than about 20 parts by weight of additive per 100 parts by weight of polymer probably will affect adversely other important physical properties, such as tensile strength and the like.

The vinyl chloride and vinylidene chloride polymers may be prepared by any method known to the art such as by emulsion, suspension, bulk or solution polymerization. The additive compounds may be mixed with the polymer emulsion, suspension, solution or bulk mass before monomer recovery and/or drying. More preferably the compounds may be mixed with dry granular or powdered vinyl halide polymers. The polymer and compound may be mixed thoroughly in granular or powder form in apparatus such as a Henschel mixer and the like. Alternatively, this step may be eliminated and the mixing done while the polymer mass is fluxed, fused and masticated to homogeneity under fairly intensive shear in or on a mixer apparatus having its metal surface in contact with the material. The fusion temperature and time will vary according to the polymer composition and level of additive compound but will generally be in the range of about 300 to 400F and 2 to 10 minutes.

Smoke retardancy may be measured using an NBS Smoke Chamber according to procedures described by Gross et al, "Method for Measuring Smoke from Burning Materials," Symposium on Fire Test Methods -- Restraint & Smoke 1966, ASTM STP 422, pp. 166-204. Maximum smoke density (Dm) is a dimensionless number and has the advantage of representing a smoke density independent of chamber volume, specimen size or photometer path length, provided a consistent dimensional system is used. Maximum rate of smoke generation (Rm) is defined in units of min- 1. Percent smoke reduction is calculated using this equation: ##EQU1## The term "Dm /gram" means maximum smoke density per gram of sample. Dm and other aspects of the physical optics of light transmission through smoke are discussed fully in the above ASTM publication.

Smoke retardancy may be measured quickly using the Goodrich Smoke-Char Test. Test samples may be prepared by dry blending polymer resin and smoke retardant additives. The blend is ground in a liquid N2 -cooled grinder to assure uniform dispersion of the smoke retardant additives in the resin. Small (about 0.3 g) samples of the polymer blend are pressed into pellets about 1/4 inch in diameter for testing. Alternatively, test samples may be prepared by blending resin, smoke retardant additives and lubricant(s) or processing aid(s) in a blender such as an Osterizer blender. The blend is milled, pressed into sheets, and cut into small (about 0.3 gram) samples for testing. The test samples are placed on a screen and burned for 60 seconds with a propane gas flame rising vertically from beneath the sample. Sample geometry at a constant weight has been found not to be significant for the small samples used in this test. A Bernz-O-Matic pencil flame burner head is used with gas pressure maintained at 40 psig. The sample is immersed totally and continuously in the flame. Smoke from the burning sample rises in a vertical chimney and passes through the light beam of a Model 407 Precision Wideband Photometer (Grace Electronics, Inc., Cleveland, Ohio) coupled with a photometer integrator. Smoke generation is measured as integrated area per gram of sample.

The vinyl chloride and vinylidene chloride polymer compositions of this invention may contain the usual compounding ingredients known to the art such as fillers, stabilizers, opacifiers, lubricants, processing aids, impact modifying resins, plasticizers, antioxidants and the like.

The following examples illustrate the present invention more fully.

EXAMPLES 1 - 6

The following recipe was used:

MATERIAL                PARTS______________________________________Polyvinyl Chloride*     100.0Polyethylene Powder Processing Aid                    1.5Additive (A)**          VariableAdditive (B)***         Variable______________________________________ *Homopolymer having an inherent viscosity of about 0.92-0.99; ASTM classification GP-4-15443. **Nickel compound selected from the group consisting of NiCl2, NiCO3, NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWO4, nickel citrate and nickel formate. The control sample contained no additive. ***Bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3, and Bi2 S3. The control sample contained no additive.

Each experimental sample was prepared by milling the recipe material on a two-roll mill for about 5 minutes at a roll surface temperature of about 320F. The milled samples were pressed into 6 in. 6 in. 0.050 in. sheets, except for examples 2 and 4, which were pressed into 6 in. 6 in. 0.075 in. sheets. Pressing was done at about 310 - 320F. using 40,000 lbs. of force applied to a 4-inch ram. The samples were given a 2-minute preheat prior to pressing for 8 minutes under full load.

The molded samples were cut into 3 in. 3 in. 0.050 in. sections, except for examples 2 and 4, which were cut into 3 in. 3 in. 0.075 in. sheets. The sections were tested using the flaming mode of the NBS Smoke Chamber Test (ASTM STP 422, pp. 166-204) described heretofore. Test results are given in Table I.

                                  TABLE I__________________________________________________________________________                  Maximum                  Rate of Smoke                           Maximum SmokeAdditive (A)         Additive (B)                  Generation                           Density per Gram ofExample(phr)    (phr)    (Rm, min- 1)                           Sample (Dm /g)                                       Smoke Reduction__________________________________________________________________________                                       (%)Control(No Additive)         (No Additive)                  556      68.6        --1    NiO (10)          111      32.9        52.0--       Bi2 O3 (10)                  209      25.4        63.0NiO (5)  Bi2 O3 (5)                   78      16.4        76.0 2*  NiO (10) --       --       33.6        51.0--       Bi2 O2 CO3 (10)                  --       25.5        62.0NiO (5)  Bi2 O2 CO3 (5)                  --       11.9        82.6NiO (7)  Bi2 O2 CO3 (3)                  --       10.8        84.3NiO (3)  Bi2 O2 CO3 (7)                  --       19.1        72.23    NiO (10) --       111      32.9        52.0--       BiBO3 (10)                   95      21.0        69.4NiO (5)  BiBO3 (5)                   98      15.4        77.6 4*  Ni2 O3 (10)         --       315      34.5        49.7--       Bi2 O2 CO3 (10)                  --       24.5        62.8Ni2 O3 (5)         Bi2 O2 CO3 (5)                  --       21.5        68.75    NiS (10) --       280      58.2        15.0--       Bi2 O2 CO3 (10)                  109      24.5        64.3NiS (5)  Bi2 O2 CO3 (5)                  128      20.1        70.76    NiWO4 (6)         --       263      41.8        39.1--       Bi2 O2 CO3 (6)                  --       20.2        70.5NiWO4 (4)         Bi2 O2 CO3 (2)                  115      19.3        71.9__________________________________________________________________________ *Sample size was 3 in.  3 in.  3 in.  0.075 in.

The above results demonstrate that the additive mixtures used in this invention are synergistic and substantially retard smoke formation during burning of rigid polyvinyl chloride in the NBS Smoke Chamber (ASTM STP 422, pp. 166-204). The results also demonstrate the smoke retardant effects of individual additives in the same test.

EXAMPLES 7 - 13

The following recipe was used:MATERIAL PARTS______________________________________Polyvinyl Chloride* 100.0Additive (A)** VariableAdditive (B)*** Variable______________________________________ *Homopolymer having an inherent viscosity of about 0.92 - 0.99; ASTM classification GP-4-15443. **Nickel compound selected from the group consisting of NiCl2, NiCO3, NiMoO4, NiO, Ni2 O3, NiS, NiSO4, NiWO4, nickel citrate and nickel formate. ***Bismuth compound selected from the group consisting of BiBO3, Bi2 O3, Bi2 O2 CO3 and Bi2 S3.

Each experimental sample was prepared by blending resin and additives in a liquid N2 -cooled grinder to assure uniform dispersion of the smoke retardant additives in the resin. Small (about 0.3 gram) samples of the polymer blend were pressed into pellets about 1/4 inch in diameter and tested using the Goodrich Smoke-Char Test described heretofore. Test results are given in Table II. .

                                  TABLE II__________________________________________________________________________Additive (A)            Additive (B)                     Smoke Formation perExample(phr)       (phr)    Gram of Sample                                 Smoke Reduction (%)__________________________________________________________________________ControlNone        None     67.4        --7    NiCl2 (10)            --       22.1        67.2--          Bi2 O2 CO3 (10)                     12.5        81.5NiCl2 (5)            Bi2 O2 CO3 (5)                      9.2        86.48    NiCO3 (10)            --       38.7        42.6--          Bi2 S3 (10)                     20.8        69.1NiCO3 (5)            Bi2 S3 (5)                     14.6        78.39    NiMoO4 (6)            --       21.4        68.2--          Bi2 O2 CO3 (6)                     27.0        59.9NiMoO4 (4)            Bi2 O2 CO3 (2)                     17.4        74.210   NiSO4 (10)            --       18.9        72.0--          Bi2 O2 CO3 (10)                     12.5        81.5NiSO4 (5)            Bi2 O2 CO3 (5)                     11.0        83.711   Nickel Citrate (10)            --       34.6        48.7--          Bi2 O.sub. 2 CO3 (10)                     12.5        81.5Nickel Citrate (5)            Bi2 O2 CO3 (5)                     10.9        83.812   Nickel Formate (10)            --       36.3        46.1--          Bi2 O2 CO3 (10)                     12.5        81.5Nickel Formate (5)            Bi2 O2 CO3 (5)                     11.9        82.313   NiO (10)    --       24.7        63.4--          Bi2 O3 (10)                     20.7        69.3NiO (5)     Bi2 O3 (5)                     10.1        85.0__________________________________________________________________________

The above results demonstrate that the defined additive mixtures substantially reduce smoke evolution during forced burning of rigid polyvinyl chloride in the Goodrich Smoke-Char Test. The results also demonstrate the smoke retardant effects of individual additives in the same test.

EXAMPLES 14 - 23

The following recipe was used:MATERIAL PARTS______________________________________Polyvinyl Chloride* 100.0Polyethylene Powder Processing Aid 1.5Smoke Retardant Additive Variable______________________________________ *Homopolymer having an inherent viscosity of about 0.92 - 0.99; ASTM classification GP-4-15443.

Each experimental sample was prepared using the same experimental preparation procedure and NBS Smoke Chamber Test as for example 1 - 6. Test results are given in Table III.

                                  TABLE III__________________________________________________________________________                Maximum                Rate of Smoke                         Maximum Smoke                Generation                         Density per GramExampleAdditive (phr)  (Rm, min- 1)                         of Sample (Dm /g)                                   Smoke Reduction__________________________________________________________________________                                   (%)ControlNone            556      68.6      --14   NiB2 (6)   460      55.2      19.515   NiI2 (5)   191      35.9      47.716   NiFe2 O4 (5)                218      18.8      72.517   Ni3 (PO4)2 (5)                274      56.8      17.218   Ni3 (PO4)2 (6)                294      32.0      53.319   NiSnO3 (6) 105      22.0      67.920   Ni2 Si (10)                451      53.4      22.121   Nickel Acetylacetonate (10)                183      45.8      33.222   BiI3 (10)   60      14.7      78.523   BiPO4.3H2 O (6)                258      25.0      63.5__________________________________________________________________________

The above results demonstrate that the defined additives substantially reduce smoke evolution during forced burning of rigid polyvinyl chloride in the NBS Smoke Chamber (ASTM STP 422, pp. 166 - 204).

EXAMPLES 24 - 32

The following recipe was used:

Each experimental sample was prepared using the same experimental preparation procedure and Goodrich Smoke/Char Test as for examples 7 - 13. Test results are given in Table IV.

                                  TABLE IV__________________________________________________________________________                Smoke Formation perExampleAdditive (phr)  Gram of Sample                            Smoke Reduction (%)__________________________________________________________________________ControlNone            67.4        --24   NiB2 (6)   60.4        10.325   NiCrO4 (10)                44.4        34.126   NiFe2 O4 (5)                25.2        62.627   Ni3 (PO4)2 (6)                40.5        39.928   NiSnO3 (6) 22.7        66.329   Ni2 Si (10)                63.1         6.430   Nickel Acetylacetonate (10)                39.6        41.231   BiI3 (10)  10.7        84.132   BiPO4.3H2 O (6)                10.9        83.8__________________________________________________________________________

The above results demonstrate that the defined additives substantially reduce smoke evolution during forced burning of rigid polyvinyl chloride in the Goodrich Smoke/Char Test.

The improved smoke retardant vinyl chloride and vinylidene chloride polymer compositions of this invention are useful wherever smoke resistance is desirable, such as in carpets, house siding, plastic components for airplane interiors, and the like. Of course, overall suitability for a particular use will depend upon other factors as well, such as comonomer type and level, compounding ingredient type and level, polymer particle size, etc.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2157997 *Jun 16, 1938May 9, 1939Goodrich Co B FMethod of treating polyvinyl halides
US2825656 *Jul 23, 1954Mar 4, 1958British CelaneseThermoplastic sheeting, etc.
US3207720 *Jun 5, 1963Sep 21, 1965Gen ElectricPolyvinyl chloride compositions cured with a metal halide
US3239482 *Mar 18, 1963Mar 8, 1966Raychem CorpFlame retardant compositions
US3326832 *Jan 21, 1964Jun 20, 1967Basf AgSelf-extinguishing plastics compositions
US3474464 *Aug 3, 1967Oct 21, 1969Grace W R & CoProcess for preparing acetylacetonates
US3513021 *Aug 24, 1966May 19, 1970Minnesota Mining & MfgElectromagnetic-sensitive recording medium
US3870679 *Apr 16, 1973Mar 11, 1975Ethyl CorpSmoke retardant vinyl halide polymers
US3883482 *Feb 1, 1974May 13, 1975Goodrich Co B FFlame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions
US3900441 *Jul 10, 1974Aug 19, 1975Armstrong Cork CoZinc and molybdenum-containing compounds as smoke depressants for poly(vinyl chloride) resin compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4143030 *Feb 22, 1977Mar 6, 1979The B. F. Goodrich CompanySmoke retardant vinyl chloride and vinylidene chloride polymer compositions
US5583172 *Oct 4, 1994Dec 10, 1996Kyowa Chemical Industry Co., Ltd.Flame retardant aid, flame retardant and flame-retardant composition
US5691404 *Jun 6, 1996Nov 25, 1997E. I. Du Pont De Nemours And CompanyFire resistant polyamide compositions
US20040242743 *Aug 21, 2002Dec 2, 2004Jean-Jacques RobinCompositions formed from chlorinated polymers and articles manufactured using these compositions
EP0128537A1 *Jun 7, 1984Dec 19, 1984The B.F. GOODRICH CompanySmoke-retarded post-chlorinated polyvinyl chloride compositions
WO2003018683A1 *Aug 21, 2002Mar 6, 2003Etienne HannecartCompositions formed from chlorinated polymers and articles manufactured using these compositions
Classifications
U.S. Classification524/382, 524/417, 524/431, 524/435, 524/174, 524/420, 524/406, 524/405, 524/404, 524/408, 524/398, 524/424, 524/423
International ClassificationC08K3/00, C08K5/098
Cooperative ClassificationC08K5/098, C08K3/0091
European ClassificationC08K3/00S4, C08K5/098
Legal Events
DateCodeEventDescription
Jul 20, 1993ASAssignment
Owner name: GEON COMPANY, THE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:B. F. GOODRICH COMPANY, THE;REEL/FRAME:006655/0825
Effective date: 19930709